Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
  • C01B3/0005—Reversible storage of hydrogen, e.g. by hydrogen getters or electrodes
  • C01B3/001—Reversible storage of hydrogen, e.g. by hydrogen getters or electrodes characterised by the uptaking media; Treatment thereof
  • C01B3/0015—Organic compounds, e.g. liquid organic hydrogen carriers [LOHC] or metalorganic compounds; Solutions thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
  • B01D15/08—Selective adsorption, e.g. chromatography
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
  • B01J20/12—Naturally occurring clays or bleaching earth
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
  • B01J20/16—Alumino-silicates
  • B01J20/18—Synthetic zeolitic molecular sieves
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
  • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
  • C01B3/22—Production of hydrogen; Production of gaseous mixtures containing hydrogen by decomposition of gaseous or liquid organic compounds
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/02—Processes for making hydrogen or synthesis gas
  • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
  • C01B2203/1205—Composition of the feed
  • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
  • C01B2203/1258—Pre-treatment of the feed
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/30—Hydrogen technology
  • Y02E60/32—Hydrogen storage

Definitions

• the present invention relates to the field of aromatic molecules capable of transporting hydrogen, and more particularly the field of the purification of said aromatic molecules capable of transporting hydrogen. 'hydrogen.
• the principle consists in fixing hydrogen on a support molecule, which is preferably and most often liquid at room temperature, in a hydrogenation step, then in releasing the fixed hydrogen, close to the place of consumption, in a dehydrogenation step.
• aromatic fluids with two or three nuclei such as for example benzyltoluene (BT) and/or dibenzyltoluene (DBT) which have already been the subject of numerous studies and of patent applications, represent molecules particularly suitable for this use.
• Patent EP2925669 thus shows the use of BT and DBT in LOHC technology, and describes the hydrogenation and dehydrogenation operations of these fluids for the storage and release of hydrogen.
• the sequence of cycles and the maintenance of performance (yield of hydrogen fixation/release) as well as the quality of the hydrogen obtained during the dehydrogenation step are key points for the economic aspect of this technology.
• the hydrogen resulting from this LOHC technology finds uses in very many fields, such as for example in fuel cells, in industrial processes, or even as fuel for means of transport (train, boats , trucks, motor cars). Any impurity present in the hydrogen, even in trace amounts, could have a negative impact both on the hydrogenation/dehydrogenation process in terms of yield, on the quality of the products manufactured or even on the yields in the end uses of the hydrogen. hydrogen produced by this technique.
• impurities are of various kinds, and may be present in more or less significant quantities.
• One class of impurities in particular consists of the oxygenated derivatives present in the fluid which undergoes the hydrogenation/dehydrogenation cycles (known as the "LOHC fluid" in the rest of this presentation), either inherently (due to the manufacturing process of the said fluid LOHC), or formed by the presence of dissolved oxygen mainly during the steps of handling the LOHC fluid, its transport, or even its transfer.
• This dissolved oxygen under hydrogenation and dehydrogenation conditions, can, depending on the operating conditions (temperature, pressure, catalyst) react with the LOHC fluid to form oxygenated derivatives.
• a group of impurities that may be present in the LOHC fluid, and which may be present and/or co-produced with hydrogen during the dehydrogenation step comprises gaseous species such as oxygen derivatives, mainly oxides, and more particularly carbon oxides (COx), nitrogen oxides (NOx) and sulfur oxides (SOx), and others, as well as mixtures thereof.
• gaseous species such as oxygen derivatives, mainly oxides, and more particularly carbon oxides (COx), nitrogen oxides (NOx) and sulfur oxides (SOx), and others, as well as mixtures thereof.
• these impurities mainly in the form of oxides as indicated above, can pollute the hydrogen produced from the dehydrogenation of the LOHC liquid, it is also possible that a more or less significant part of these impurities remain in the LOHC fluid, with a risk of accumulation of impurities in the LOHC fluid after numerous hydrogenation/dehydrogenation cycles.
• a first objective of the present invention is the production of pure hydrogen by dehydrogenation of a fluid.
• Another objective is the production of hydrogen comprising as low a level of impurities as possible, by dehydrogenation of a fluid.
• Another objective is to provide a fluid capable of being dehydrogenated to supply hydrogen comprising a level of impurities that is as low as possible, said fluid being able to be reused in a large number of hydrogenation/dehydrogenation cycles.
• Another Another objective is to improve the production of hydrogen by dehydrogenation of fluids, in terms of purity, yield, and manufacturing costs, among others.
• the invention relates to a method for producing hydrogen from a liquid capable of being engaged in at least one hydrogenation/dehydrogenation cycle, said method comprising at least one step in which said liquid is brought into contact with a filtering agent.
• an LOHC liquid for example an aromatic liquid, optionally at least partially or totally hydrogenated
• an LOHC liquid for example an aromatic liquid, optionally at least partially or totally hydrogenated
• the filtering agents which can be used in the context of the present invention can be of all types and are well known to those skilled in the art.
• the filtering agents which have proved to be the most suitable are the adsorbent filtering agents, and more particularly the filtering agents comprising one or more compounds chosen from minerals based on silicates, carbonates, carbon, as well as mixtures of two or more of these minerals in all proportions.
• adsorbent filtering agents and more particularly the filtering agents comprising one or more compounds chosen from minerals based on silicates, carbonates, carbon, as well as mixtures of two or more of these minerals in all proportions.
• inorganic or organic filtering agents and in particular those chosen from clays, zeolites, diatomaceous earth, ceramics, carbonates, and carbon derivatives, as well as mixtures of two or more of them, in any proportion.
• clays including silicates, and for example magnesium silicates, such as and without limitation, attapulgites, montmorillonites, selenites, bentonites, talcs, and others,
• Silicates in particular clays and zeolites, have proved to be particularly effective for the purposes of the process according to the present invention. Silicates have in fact shown themselves to be very particularly suitable for the elimination, or at least for the significant reduction, of the impurities present in a liquid capable of being engaged in at least one hydrogenation/dehydrogenation cycle for the production of hydrogen.
• Attapulgite Microsorb ® 16/30 LVM from BASF (example of alumino-magnesian clay with the chemical formula (Mg, Al ) 5 SÎ 8 0 22 (OH) 4 , S1O2)
• Amcol Rafinol 900 FF from Minerals Technologies
• Amcol Rafinol 920 FF from Minerals Technologies
• Amcol Mineral Bent aluminum hydrosilicate
• Siliporite ® in particular MK30B0 and MK30B2
• ARKEMA preparations based on zeolite of the alumino silicate type
• the liquid capable of being hydrogenated/dehydrogenated and which is brought into contact with a filtering agent can be any type of liquid, optionally at least partially hydrogenated, see totally hydrogenated, and preferably at least partially hydrogenated, see totally hydrogenated, and is most often an LOHC fluid, as previously defined.
• LOHC fluids which are liquid at ambient temperature and pressure (25° C., 1 atmosphere) are preferred, for obvious reasons of ease of handling and transport.
• the LOHC fluid in its completely dehydrogenated form, is a fluid comprising at least one aromatic nucleus
• the LOHC fluid can be derived from petroleum products and/or products synthesized from petroleum products.
• the LOHC fluid, and which comprises at least one aromatic nucleus, in its totally dehydrogenated form can come from renewable products and/or from products synthesized from renewable products.
• the fluid of the present invention may comprise one or more fluids, in the form of mixtures and for example a mixture comprising one or several fluid(s) derived from petroleum products and one or more fluid(s) derived from renewable products.
• fluids derived from petroleum products is meant, within the meaning of the present invention, the products resulting from the separation and/or purification of petroleum, but also the compounds resulting from the synthesis of compounds bearing the nucleus(x ) aromatic(s) of petroleum origin.
• fluids from renewable products is meant, within the meaning of the present invention, products from biomass, and in particular from the extraction of wood (for example lignin) and resinous products, as well as compounds from syntheses of renewable products.
• the fluid, called LOHC fluid which can be used in the method of the present invention corresponds to the general formula (1):
• a and B identical or different, represent independently of each other, an aromatic ring, optionally totally or partially hydrogenated, optionally comprising at least, and preferably, one heteroatom, and optionally substituted by one or more hydrocarbon radicals , saturated or partially or totally unsaturated, comprising from 1 to 20 carbon atoms, preferably from 1 to 18 carbon atoms, more preferably from 1 to 12 carbon atoms, better still from 1 to 10 carbon atoms, even better still from 1 to 6 carbon atoms, typically 1 to 3 carbon atoms,
• R and R' are chosen independently of each other, from hydrogen and a hydrocarbon radical, saturated or partially or totally unsaturated, containing from 1 to 6 carbon atoms, preferably from 1 with 3 carbon atoms,
• - R represents a hydrocarbon radical, saturated or partially or totally unsaturated, containing from 1 to 6 carbon atoms, preferably from 1 to 3 carbon atoms, - m represents an integer between 1 and 4 bounds inclusive, and
• aromatic ring means aromatic hydrocarbon monocycles and aromatic hydrocarbon polycycles, comprising from 6 to 20 carbon atoms, among which one or more of them may be heteroatoms chosen from oxygen, sulfur and nitrogen, preferably from sulfur and nitrogen, and more preferably nitrogen.
• polycycle is meant the rings defined above, fused or condensed, for example two, or more preferably two or three or four, more preferably two or three, for example two, fused or condensed rings.
• the LOHC fluid of formula (1) defined above is part of the family of alkylbenzenes, optionally partially or totally hydrogenated.
• the groups (AX) can be identical or different.
• n is different from 0 and B is substituted by a hydrocarbon radical.
• said hydrocarbon radical is an alkyl radical comprising from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms and preferably the alkyl radical is the methyl radical.
• in the fluid is an alkyl radical comprising from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms and preferably the alkyl radical is the methyl radical.
• n is equal to 0 and the organic liquid of formula (1) is generally chosen from linear alkylbenzenes, optionally totally or partially hydrogenated, and branched alkylbenzenes, optionally totally or partially hydrogenated, such as by example and in a nonlimiting manner alkylbenzenes, and optionally totally or partially hydrogenated homologs, in which the alkyl part comprises from 10 to 20 carbon atoms.
• alkylbenzenes include, still without limitation, decylbenzene, dodecylbenzene, octadecylbenzene, as well as their optionally totally or partially hydrogenated homologs, to name only a few of them.
• the LOHC fluids corresponding to the general formula (1) above can be used alone or in mixtures of two or more of them in all proportions.
• the LOHC fluid used in the method of the present invention may contain a compound bearing at least one aromatic radical, optionally totally or partially hydrogenated, or a mixture of two or more compounds carrying at least one aromatic radical, optionally totally or partially hydrogenated.
• the LOHC fluid used in the process of the invention is liquid at ambient temperature and ambient pressure.
• the LOHC fluid is chosen from benzyltoluene (BT), dibenzyltoluene (DBT), their partially or totally hydrogenated homologs, as well as their mixtures in all proportions.
• BT benzyltoluene
• DBT dibenzyltoluene
• the LOHC fluid is chosen from the organic fluids sold by Arkema under the trade names of the Jarytherm ® range.
• LOHC fluids and partially or totally hydrogenated counterparts, suitable for the purposes of the present invention are, for example, those marketed by the company Eastman, and in particular under the trade name Marlotherm®.
• Marlotherm® As still other examples of LOHC fluids suitable for the purposes of the present invention, mention may be made of:
• DPE diphenylethane
• 1,1-DPE CAS 612-00-0
• 1,2-DPE CAS 103-29-7
• their mixtures in particular CAS 38888-98 -1
• organic liquids being commercially available or described in the literature, for example in the document EP0098677,
• PXE - phenylxylylethane
• PEPE - phenylethylphenylethane
• CAS 6196-94-7 - phenylethylphenylethane
• the present invention relates to a method for producing hydrogen from a liquid capable of being engaged in at least one hydrogenation/dehydrogenation cycle, said method comprising at least one step in which said liquid is freed impurities generated during said hydrogenation/dehydrogenation cycle by contacting with a filtering agent.
• the process of the present invention is therefore not a process for purifying the hydrogen produced by dehydrogenation of the LOHC liquid, but a process for producing high purity hydrogen by bringing the LOHC liquid into contact with a filtering agent. entering the hydrogenation and dehydrogenation cycles.
• this operation of bringing into contact with the filtering agent can be carried out one or more times, repetitively or not, preferably repetitively.
• the operation of bringing the LOHC liquid into contact with the filtering agent can be carried out as much as necessary and after a number of dehydrogenation and/or hydrogenation operations ranging from 1 to 5000, preferably 2.
• the external supply of a quantity of LOHC liquid may also comprise one or more steps, well known to those skilled in the art, of purification of the hydrogen produced by dehydrogenation of the LOHC liquid.
• the bringing into contact of the LOHC liquid with the porous filtering agent can be carried out according to any method well known to those skilled in the art, continuously or in batch, and for example by passage, forced (pumps) or by gravity. , liquid through said filtering agent, such as in a packed column, or even by simple contact in a reactor, such as a reactor equipped or not with a stirring system, and the like.
• the duration of contacting can vary in large proportions, in particular according to the nature and the quantity of the impurities to be eliminated, the nature and the quantity of the porous filtering agent used, the nature and the quantity of liquid to be purified, and the type of contacting system used. In addition, the duration of contacting varies according to the temperature and the pressure applied.
• the temperature at which the liquid is brought into contact with the porous filtering agent is generally between 0° C. and 100° C., preferably between 5° C. and 80° C., more preferably between 10° C. and 50°C.
• the contacting is advantageously carried out without external heating or cooling, for example in a range between 15° C. and 35° C.
• the pressure at which the liquid is brought into contact with the porous filter medium is generally atmospheric pressure or even under slight overpressure or underpressure.
• the bringing into contact is advantageously carried out under atmospheric pressure, or even slight overpressure, in particular overpressure resulting from the circulation of the liquid through the said filtering medium.
• the contacting step can be carried out under air, or in the absence of air or under an inert atmosphere (for example nitrogen, argon, and the like).
• the treatment of the liquid can be carried out either before the stage of hydrogenation of the liquid, or before the stage of dehydrogenation (stage of hydrogen production proper) or even before the stage hydrogenation of the liquid and before the dehydrogenation step.
• the purification step by bringing it into contact with the filtering agent can advantageously be carried out by the supplier of the organic liquid LOHC.
• the invention thus makes it possible not only to obtain hydrogen of improved purity but also the possibility of increasing the number of hydrogenation/dehydrogenation cycles that can be carried out with the same organic liquid LOHC, which liquid can thus be recycled. thanks to the purification steps according to the invention.
• the step of purifying the organic liquid by bringing it into contact with the filtering agent is carried out before the dehydrogenation step.
• the purification of the organic liquid LOHC is carried out before the hydrogenation step and before the dehydrogenation step to limit the presence of oxygenated derivatives in the partially to totally hydrogenated organic liquid.
• the present invention relates to the use of a filtering agent as defined above for the purification of a liquid capable of being engaged in at least one hydrogenation/dehydrogenation cycle, as indicated previously.
• a filtering agent as defined above for the purification of a liquid capable of being engaged in at least one hydrogenation/dehydrogenation cycle, as indicated previously.
• Example 1 11 g of a filtering agent and 350 g of organic liquid LOHC are introduced into a vacuum flask. The contacting is carried out for a period of 16 hours with magnetic stirring, under nitrogen.
• DBT DBT Jarytherm ® marketed by Arkema
• organic liquid LOHC organic liquid LOHC.
• DBT is added 0.1% by weight of dicyclohexylmethanol (Sigma-Aldrich supplier), and the whole and brought into contact with a filtering agent.
• the test is performed with the following filter media: Attapulgite Microwave sorb® 16/30 LVM BASF and Siliporite ® molecular sieve MK30B0 (supplier ARKEMA) [0055] Following contacting with stirring for 16 hours, filtered under vacuum on Büchner to retain the solids. The filtered liquid is then analyzed (liquid chromatography).
• the level of residual dicyclohexylmethanol impurity is of the order of 0.02% by weight or less, thus demonstrating the effectiveness of the filtering agent for the purification of a fluid capable of being engaged in at least one cycle. hydrogenation/dehydrogenation.

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• 2020
  • 2020-07-10 FR FR2007313A patent/FR3112339B1/fr active Active
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